Pyrethrins and piperonyl butoxide adsorption to soil organic matter

The adsorption and mobility of pyrethrins (Pys), the major insecticidal components obtained from the pyrethrum daisy Tanacetum cinerariifolium, and piperonyl butoxide (PBO), a pyrethrum synergist, were determined in soil using batch-equilibrium and reverse-phase thin-layer chromatographic techniques. Two soil management practices were used, soil mixed with yard waste compost (COM) at 50 t acre(-1) on dry weight basis and no-mulch (NM) bare soil. Adsorption isotherm experiments were carried out using known concentrations of Pys (Py-I and Py-II) and PBO mixed with known amounts of COM or NM soil at constant temperature and pressure until equilibrium was attained. Pys and PBO in soil extracts were purified and concentrated using solid-phase extraction cartridges containing C18-octadecyl bonded silica. Pys and PBO residues were quantified using a high-performance liquid chromatograph equipped with a UV detector. Adsorption studies showed that compost amended soil adsorbed more Pys and PBO than native (NM) soil. Py-I adsorption was greater than Py-II and PBO. Adsorption of Pys and PBO to humic and fulvic acids was also studied by reverse-phase thin layer chromatography (RPTLC). Results indicated that humic acid, a significant component of organic matter, reduced Pys and PBO mobility. Pys and PBO mobility decreased as the concentration of humic acid in the mobile phase increased.     

Dissipation and residues of dimethyl disulfide in tomatoes and soil under greenhouse and open field conditions

Abstract

Tomatoes have been widely planted in greenhouses and fields in China. Soil-borne diseases are more harmful to tomatoes than other types of diseases. Dimethyl disulfide (DMDS) was used as a novel fumigant instead of methyl bromide to control soil-borne diseases. To assess the safety of DMDS for use on tomatoes, its dissipation and terminal residues were investigated at three different locations under greenhouse and open field conditions. The QuEChERS method was simplified using gas chromatography with mass spectrometry detection and combined with liquid-liquid extraction purification to allow determination of DMDS levels in both the tomatoes and the soil. The average recovery of the method was between 85.3 and 98.6%, with the relative standard deviation (RSD) ranging from to 1.9–10.3%. The dissipation and terminal residues of DMDS in the tomatoes and the soil were analyzed using the method, the results of which showed that the half-life of DMDS ranged from 0.3–6.5 d in the soil at three different locations. The terminal residues of DMDS in the tomatoes and the soil were not detected. This study provided data that the Chinese government can use to support appropriate and safe guidance for the use of DMDS on agriculture.     

Translocation of aged cyclodiene insecticide residues from soil into forage crops and pastures at various growth stages under field conditions.

Field trials were conducted to measure translocation of pesticides by summer and winter forage/pasture species from soil containing aged residues of heptachlor and, to a lesser extent, dieldrin. Substantial amounts of heptachlor epoxide, and lesser amounts of gamma-chlordane were translocated to plants from contaminated soil. Residue levels varied with crop species and stage of plant development. In summer crops residues were higher in soybean > cowpeas > lab-lab > Sorghum > millet > sweet saccaline at the grazing and mature stages. Compared to glasshouse studies undertaken previously, residues in crops grown under field conditions were much lower. This apparently reflects the lower soil moisture levels and the reduced rates of translocation. Heptachlor residues in winter crops were highest in Saia oats > Berseem clover > Haifa clover > Cassia oats > Tetila ryegrass > Schooner barley > Shaftal clover > Hunter river lucerne at the grazing stage. There were no detectable levels in barley and oats at the mature stage. No dieldrin residues were translocated into the various crop species.     

Synergism of MGK-264 and piperonyl butoxide on the toxicity of plant derive molluscicides

The binary mixture of ethanolic extract of powder, hecogenin, tigogenin, seed powder and thymol with synergiats MGK-264 and piperony butoxide in a 1:5 ratio were used against the . It was observed that the toxic effect of these mixtures were time and dose dependent. The binary mixtures of plant molluscicides with synergist were more toxic with respect to the independent toxicity of these plant molluscicides. Maximum synergistic action (10 fold) of MGK-264 and piperonyl butoxide was observed with hecogenin.     

Effects of DDT and piperonyl butoxide on the metabolic alterations in pigeon (columba livia)

Abstract

Effect of acute doses of technical grade of dichloro diphenyl trichloro ethane (DDT) and piperonyl butoxide (PB) on hepatic micro‐somal cytochrome P₄₅₀ (Cyt. P450) and cytosolic glutathione‐S‐transferase (GST) activity in pigeon were studied after 24 hours of treatment. A completely reverse trend of changes in Cyt. P450 and GST activity were found as increase in Cyt. ?450 paralleled with decrease in GST activity following exposure to DDT. However, intensity of changes in Cyt. P450 was greater than that of GST. A dose dependent decrease in Cyt. ?450 and GST activity was observed after PB treatment. The study may, therefore, throw some light on metabolic alterations in wild birds resulting from environmental pollution by DDT and allied chemicals.     

Dissipation,residues, and risk assessment of imidacloprid in Zizania latifolia and purple sweet potato under field conditions using LC-MS/MS

A shortened version of Quick, Easy, Cheap, Effective, Rugged, and Safe method (QuEChERS) for determining the dissipation and residue of imidacloprid present in Zizania latifolia and purple sweet potato was established by using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The average recoveries of imidacloprid in the two crops ranged from 82.12 to 113.79%, with relative standard deviation (RSD) of <7.32%. The dissipation dynamics of imidacloprid in Z. latifolia plants and purple sweet potato plants followed first-order kinetics, with half-lives of 3.2–5.5?days in each of sampling locations. The terminal imidacloprid residues in Z. latifolia and purple sweet potato at each of location were <0.005–0.120?mg kg^?1. According to the risk assessment results, both the acute dietary risk quotient and chronic dietary risk quotient values were <1, indicating that imidacloprid is unlikely to pose health risks to humans with normal recommended use. The present study may serve as a valuable reference for the safe and reasonable use of imidacloprid in Z. latifolia and purple sweet potato fields.     

Effects of DDT and piperonyl butoxide on the metabolic alterations in pigeon (Columbia livia)

Effect of acute doses of technical grade of dichloro diphenyl trichloro ethane (DDT) and piperonyl butoxide (PB) on hepatic microsomal cytochrome P450 (Cyt. P450) and cytosolic glutathione-S-transferase (GST) activity in pigeon were studied after 24 hours of treatment. A completely reverse trend of changes in Cyt. P450 and GST activity were found as increase in Cyt. P450 paralleled with decrease in GST activity following exposure to DDT. However, intensity of changes in Cyt. P450 was greater than that of GST. A dose dependent decrease in Cyt. P450 and GST activity was observed after PB treatment. The study may, therefore, throw some light on metabolic alterations in wild birds resulting from environmental pollution by DDT and allied chemicals.     

Translocation of aged cyclodiene insecticide residues from soil into forage crops and pastures at various growth stages under field conditions

Abstract

Field trials were conducted to measure translocation of pesticides by summer and winter forage/pasture species from soil containing aged residues of heptachlor and, to a lesser extent, dieldrin. Substantial amounts of heptachlor epoxide, and lesser amounts of y‐chlordane were translocated to plants from contaminated soil. Residue levels varied with crop species and stage of plant development. In summer crops residues were higher in soybean> cowpeas>lab‐lab>Sorghum>millet>sweet saccaline at the grazing and mature stages.

Compared to glasshouse studies undertaken previously, residues in crops grown under field conditions were much lower, this apparently reflects the lower soil moisture levels and the reduced rates of translocation.

Heptachlor residues in winter crops were highest in Saia oats > Berseem clover > Haifa clover > Cassia oats > Tetila ryegrass > Schooner barley > Shaftal clover > Hunter river lucerne at the grazing stage. There were no detectable levels in barley and oats at the mature stage. No dieldrin residues were translocated into the various crop species.     

Ivermectin dissipation and movement from feces to soil under field conditions

The aim of this work was to evaluate the fate of ivermectin (IVM) at two concentrations in cattle feces and its movement to the nearby soil and plants. Feces were spiked with IVM at two levels: 3000 ng g^?1 (high group, HG) and 300 ng g^?1 (low group, LG). Artificial dung pats were prepared and deposited in an experimental field area. Feces and underlying soil were sampled up to 60 days post-deposition (dpd). As an additional analysis, grasses growing around the pats were sampled at 30 and 60 dpd. Ivermectin concentrations in all matrices were determined by HPLC. Mean IVM fecal concentrations were in the range between 3901.9 ng g^?1 and 2419.2 ng g^?1 (high group) and 375.3 ng g^?1 and 177.49 ng g^?1 (low group). Mean times for 50% and 90% dissipation were 88.23 and 293.03 days (HG) and 39.1 and 129.9 days (LG). Soil concentrations ranged from 26.1 ng g^?1 to 71.1 ng g^?1 (HG) and 3.4 to 5.9 ng g^?1 (LG); in plants, concentrations were between 71.4 and 380.8 ng g^?1 and 5.40 and 51.8 ng g^?1 in HG and LG, respectively. These results confirm that IVM moves from feces to the underlying soil as well as to nearby plants. The potential risk of detrimental effects on soil organisms and the impact on herbivorous animals should be further evaluated.     

Degradation of silicone polymer in a field soil under natural conditions

Silicone polymers (PDMS = polydimethylsiloxane) are used in numerous consumer and industrial products. Our previous work showed that they will degrade in soil under laboratory conditions. This paper investigates PDMS degradation in the field. Four soil plots (each 2.44 m x 2.44 m) in Michigan were sprayed in May, 1997, with aqueous emulsion to achieve nominal soil PDMS concentrations of 0 (control), 215 (low), 430 (medium), and 860 (high) microg/g. Over the following summer, soil cores (0-5 and 5-10 cm) were collected every two weeks and analyzed for decrease in-total soil PDMS, and decrease in molecular weight of remaining PDMS. PDMS concentrations decreased 50% in 4.5, 5.3, and 9.6 weeks for the low, medium, and high treatments, respectively. Degradation rates were 0.26 (low), 0.44 (medium), and 0.44 (high) g PDMS/m2 day, indicating that degradation capacity of the soil was exceeded by the High treatment. Dimethylsilanediol (DMSD), the main degradation product, was detected in most samples at <5% of original PDMS. This is consistent with laboratory data showing biodegradation and volatilization of DMSD. Deeper sampling (to 20 cm) found only trace amounts of DMSD, and minor downward movement of the polymer. Respraying and subsequent analysis of one plot with a medium treatment in late August showed slow PDMS degradation during the cool, wet fall, followed by a 40% decrease over winter and extensive degradation during the summer of 1998. The study thus shows that PDMS will degrade under field conditions as predicted from laboratory experiments.     

The toxicity of pyrene in the fish : Synergism by piperonyl butoxide and by ultraviolet light

A saturated solution of pyrene in water was not toxic to the fish , even in the presence of ultraviolet light. A survival curve possessing one minimum, and therefore defining two LC₅₀ values, was obtained when fish placed in water containing increasing amounts of a pyrene solution in dimethylsulfoxide were exposed to ultraviolet light after a short incubation period. The phototoxicity was linked to the presence of undissolved pyrene. A normal survival curve with only one LC₅₀ value was found when pyrene was solubilized with the surfactant Tween-20. Practically no phototoxicity was produced when the pyrene mixtures were filtered before use, or when a saturated aqueous solution of pyrene was used. Piperonyl butoxide, present at a concentration where it was not toxic, synergized the toxicity of pyrene . The environmental significance of this observation may be considerable.     

Effect of organic amendment on degradation and formation of bound residues of methabenzthiazuron in soil under constant climatic conditions

Abstract

The degradation of [phenyl‐U‐¹⁴C]methabenzthiazuron (MBT) and formation of bound residues in the surface soil of an orthic luvisol were studied under constant climatic conditions (20°C, 40 % of maximum water holding capacity). In two treatments (with and without preincubation in the soil) maize straw was amended at a rate of 1.5 g/100 g dry soil in addition to the application of MBT. The mineralization of uniformly labeled maize straw was studied simultaneously. In additional flasks, MBT was incubated at 0, 10 and 30°C with and without addition of maize straw.

The turnover of the amended maize straw led to an enhanced dissipation of MBT which was mainly due to the formation of bound residues. This corresponded to a higher microbial activity in the soil after straw amendment and the intensive mineralization of the radiolabeled maize straw. About 2–3 % of the applied radioactivity from the radiolabeled maize straw was measured in the soil microbial biomass 10 and 40 days after application whereas ¹⁴C from MBT was only incorporated into soil microbial biomass in the treatments with straw amendment.

Within the bound residue fractions relatively more radioactivity was measured in fulvic and humic acids after straw amendment. Increasing temperatures promoted the dissipation of MBT and the formation of bound residues in both treatments, but without amendment of maize straw these effects were far less pronounced. The laboratory scale degradation experiment led to similar results as were found in a corresponding lysimeter study. Differences that were observed could be explained by different temperature regimes of the experiments and time of aging in soil.     

Dissipation and translocation of saisenxin in tobacco and soil under conventional field and controlled laboratory conditions

Abstract

The aim of this investigation was to investigate the fate and translocation characteristics of saisenxin (SSX), a novel organic zinc fungicide, in the environment and tobacco plants under conventional field and laboratory conditions. A rapid and sensitive analytical technique based on high-performance liquid chromatography was used for determination of SSX, in soil samples and tobacco leaf, stem and root samples. The method had satisfactiry linearity (R^2?=?0.9999) and the limits of detection and of quantitation of the target compound were 0.06 and 0.20?mg kg^?1, respectively. The average recoveries were in the range of 89.74–94.24% in soil, leaf, stem and root samples, with relative standard deviations of <8%. For conventional field trials, the half-life (t_1/2) of SSX was 5.9–6.5 days in soil and 4.8–5.3 days in tobacco leaves; the corresponding values under controlled laboratory conditions were extended to 7.1 and 7.6?days. The translocation factor (TF) values were in the range of 0–2.25 and 0–0.25 for foliage and root irrigation treatments, respectively. The TFs of SSX in tobacco indicated that tobacco had a high ability to transfer SSX upward.     

Dissipation pattern of flubendiamide residues on capsicum fruit (Capsicum annuum L.) under field and controlled environmental conditions

This investigation was undertaken to compare the dissipation pattern of flubendiamide in capsicum fruits under poly-house and open field after giving spray applications at the recommended and double doses of 48 g a.i. ha^?1 and 96 g a.i. ha^?1. Extraction and purification of capsicum fruit samples were carried out by the QuEChERS method. Residues of flubendiamide and its metabolite, des-iodo flubendiamide, were analyzed by high-performance liquid chromatography–photodiode array, and confirmed by liquid chromatography–mass spectrometry/mass spectrometry. Limit of quantification of the method was 0.05 mg kg^?1, and recovery of the insecticides was in the range of 89.6–104.3%, with relative standard deviation being 4.5–11.5%. The measurement uncertainty of the analytical method was in the range of 10.7–15.7%. Initial residue deposits of flubendiamide on capsicum fruits grown under poly-house conditions were (0.977 and 1.834 mg kg^?1) higher than that grown in the field (0.665 and 1.545 mg kg^?1). Flubendiamide residues persisted for 15 days in field-grown and for 25 days in poly-house-grown capsicum fruits. The residues were degraded with the half-lives of 4.3–4.7 and 5.6–6.6 days in field and poly-house respectively. Des-iodo flubendiamide was not detected in capsicum fruits or soil. The residues of flubendiamide degraded to below the maximum residue limit notified by Codex Alimentarius Commission (FAO/WHO) after 1 and 6 days in open field, and 3 and 10 days in poly-house. The results of the study indicated that flubendiamide applied to capsicum under controlled environmental conditions required longer pre-harvest interval to allow its residues to dissipate to the safe level.     

Transport of simazine in unsaturated sandy soil and predictions of its leaching under hypothetical field conditions

The potential contamination of groundwater by herbicides is often controlled by processes in the vadose zone, through which herbicides travel before entering groundwater. In the vadose zone, both physical and chemical processes affect the fate and transport of herbicides, therefore it is important to represent these processes by mathematical models to predict contaminant movement. To simulate the movement of simazine, a herbicide commonly used in Chilean vineyards, batch and miscible displacement column experiments were performed on a disturbed sandy soil to quantify the primary parameters and processes of simazine transport. Chloride (Cl(-)) was used as a non-reactive tracer, and simazine as the reactive tracer. The Hydrus-1D model was used to estimate the parameters by inversion from the breakthrough curves of the columns and to evaluate the potential groundwater contamination in a sandy soil from the Casablanca Valley, Chile. The two-site, chemical non-equilibrium model was observed to best represent the experimental results of the miscible displacement experiments in laboratory soil columns. Predictions of transport under hypothetical field conditions using the same soil from the column experiments were made for 40 years by applying herbicide during the first 20 years, and then halting the application and considering different rates of groundwater recharge. For recharge rates smaller than 84 mm year(-1), the predicted concentration of simazine at a depth of 1 m is below the U.S. EPA's maximum contaminant levels (4 microg L(-1)). After eight years of application at a groundwater recharge rate of 180 mm year(-1) (approximately 50% of the annual rainfall), simazine was found to reach the groundwater (located at 1 m depth) at a higher concentration (more than 40 microg L(-1)) than the existing guidelines in the USA and Europe.     

Effects of metal-contaminated soil on the performance of young trees growing in model ecosystems under field conditions

Young Populus tremula, Salix viminalis, Betula pendula and Picea abies trees were grown together in large open-top chambers. The treatments were: without or with (Cu/Zn/Cd/Pb=640/3000/10/90 mg kg-1) metal contamination in the topsoil, irrigation pH 3.5 or 5.5, and acidic or calcareous subsoil. Growth, metal allocation to foliage and wood, as well as leaf gas exchange were measured. Biomass was reduced in P. tremula and B. pendula by the metal-contaminated topsoil relative to uncontaminated topsoil, whereas in P. tremula photosynthesis and transpiration were decreased. These effects were related to the elevated foliar Zn accumulation in P. tremula. S. viminalis showed a significant reduction in growth and an increased Zn and Cd accumulation on acidic vs. calcareous subsoil. Acidic irrigation produced only a few significant effects. P. abies showed the lowest metal uptake and no growth response to metal contamination.     

Mitigation of dimethazone residues in soil and runoff water from agricultural field

Dimethazone, also known as clomazone [2-[(2-chlorophenyl) methyl]- 4,4-dimethyl-3-isoxaolidinone] is a pre-emergent nonionic herbicide commonly used in agriculture. A field study was conducted on a silty-loam soil of 10 % slope to monitor off-site movement and persistence of dimethazone in soil under three management practices. Eighteen plots of 22 x 3.7 m each were separated using stainless steel metal borders and the soil in six plots was mixed with municipal sewage sludge (MSS) and yard waste (YW) compost (MSS+YW) at 15 t acre?1 on dry weight basis, six plots were mixed with MSS at 15 t acre?1, and six unamended plots (NM) were used for comparison purposes. The objectives of this investigation were to: (i) monitor the dissipation and half-life (T?/?) of dimethazone in soil under three management practices; (ii) determine the concentration of dimethazone residues in runoff and infiltration water following natural rainfall events; and (iii) assess the impact of soil amendments on the transport of NO?, NH?, and P into surface and subsurface water. Gas chromatography/mass spectrometery (GC/MS) analyses of soil extracts indicated the presence of ion fragments at m/z 125 and 204 that can be used for identification of dimethazone residues. Intitial deposits of dimethazone varied from 1.3 μg g?1 dry native soil to 3.2 and 11.8 μg g?1 dry soil in MSS and MSS+YW amended soil, respectively. Decline of dimethazone residues in the top 15 cm native soil and soil incorporated with amendments revealed half-life (T?/?) values of 18.8, 25.1, and 43.0 days in MSS+YW, MSS, and NM treatments, respectively. Addition of MSS+YW mix and MSS alone to native soil increased water infiltration, lowering surface runoff water volume and dimethazone residues in runoff following natural rainfall events.     

Dissipation of spiromesifen and spiromesifen-enol on tomato fruit,tomato leaf,and soil under field and controlled environmental conditions

Dissipation of spiromesifen and its metabolite, spiromesifen-enol, on tomato fruit, tomato leaf, and soil was studied in the open field and controlled environmental conditions. Sample preparation was carried out by QuEChERS method and analysis using LC-MS/MS. Method validation for analysis of the compounds was carried out as per “single laboratory method validation guidelines.” Method validation studies gave satisfactory recoveries for spiromesifen and spiromesifen-enol (71.59–105.3%) with relative standard deviation (RSD) < 20%. LOD and LOQ of the method were 0.0015 μg mL^?1 and 0.005 mg kg^?1, respectively. Spiromesifen residues on tomato fruits were 0.855 and 1.545 mg kg^?1 in open field and 0.976 and 1.670 mg kg^?1 under polyhouse condition, from treatments at the standard and double doses of 125 and 250 g a.i. ha^?1, respectively. On tomato leaves, the residues were 5.64 and 8.226 mg kg^?1 in open field and 6.874 and 10.187 mg kg^?1 in the polyhouse. In soil, the residues were 0.532 and 1.032 mg kg^?1 and 0.486 and 0.925 mg kg^?1 under open field and polyhouse conditions, respectively. The half-life of degradation of spiromesifen on tomato fruit was 6–6.5 days in the open field and 8.1–9.3 days in the polyhouse. On tomato leaves, it was 7–7.6 and 17.6–18.4 days and in soil 5.6–7.4 and 8.4–9.5 days, respectively. Metabolite, spiromesifen-enol, was not detected in any of the sample throughout the study period. Photodegradation could be the major route for dissipation of spiromesifen in the tomato leaves, whereas in the fruits, it may be the combination of photodegradation and dilution due to fruit growth. The results of the study can be utilized for application of spiromesifen in plant protection of tomato crop under protected environmental conditions.     

Persistence and movement of chlorbromuron in potato soil.

Movement and persistence of chlorbromuron applied at rates of 1.5, 3, and 6 kg a.i./ha was studied in a New Brunswick potato soil for one growing season. Most of the chlorbromuron remained in the 0 - 2.5 cm soil depth with slight residues in the 2.5 - 5, 5 - 7.5, and 7.5 - 10 cm depths. After 47 days the chlorbromuron residues had dropped to 40%, then gradually levelled off to 25% at the end of the season. Chlorbromuron was determined directly by electron capture gas chromatography using a short glass column of 3% OV-210.     

Persistence of fluazinam in soil under boreal conditions

Abstract

Fluazinam, a widely used pesticide in conventional potato cultivation, is effective against epidemics of the fungal disease late blight. To assess fluazinam persistence in soil, laboratory experiments were conducted with fluazinam added to soil as a pure chemical or contained in the commercial product Shirlan^®. In a follow-up experiment, the persistence was monitored under constant temperature and water content conditions during a maximum period of 1?year. In an annual climatic rotation experiment, fluazinam added to soil was exposed to the year-round temperature and water content conditions occurring in the boreal zone. A third experiment was undertaken to clarify the effect of soil organic matter (SOM) on the recovery of fluazinam. In the follow-up and annual climatic rotation experiments, more than half of the added fluazinam was recovered after 1?year of incubation. The estimated half-life of fluazinam ranged between 355 and 833?days. The degradation of fluazinam was enhanced by an abundance of SOM, a warm temperature, and wetness. Additionally, in over half of soil samples collected from fields where potato had been intensively cultivated for many years, varying concentrations of fluazinam were detected. Fluazinam can carry over to the next growing season in professional potato production.